CN102795667B - Method for preparing carbon-coated nanometer molybdenum dioxide material - Google Patents
Method for preparing carbon-coated nanometer molybdenum dioxide material Download PDFInfo
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- CN102795667B CN102795667B CN201210313016.9A CN201210313016A CN102795667B CN 102795667 B CN102795667 B CN 102795667B CN 201210313016 A CN201210313016 A CN 201210313016A CN 102795667 B CN102795667 B CN 102795667B
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Abstract
The invention relates to a method for preparing a carbon-coated nanometer molybdenum dioxide material. The method comprises the steps of: adding reducing sugar and a molybdenum precursor in a solvent to form a mixture, wherein the proportion of the reducing sugar to the molybdenum precursor is 1:1-10: 1 according to the ratio of the mole number of the reducing sugar to the mole number of M06+, and the mass ratio of the sum of the mass of the sugar and the molybdenum to the solvent is 1:2-1:50; filling the mixture into a reaction kettle and crystallizing at a heating temperature of 100 DEG C to 250 DEG C; after crystallizing for 2 h to 48 h, cooling the reaction kettle to a room temperature so as to obtain a crystallized product; cleaning the crystallized product by using water or dimethyl formamide; and then centrifugally separating to obtain the carbon-coated nanometer molybdenum dioxide material. The reducing sugar which is green, environment-friendly and easy to obtain not only serves as a mild reductant of the molybdenum precursor, but also serves as a precursor of carbon, so that a small-size carbon-coated nanometer molybdenum dioxide material with adjustable size can be obtained by one step by utilizing a water heating or solvent heating way.
Description
Technical field
The invention belongs to the synthetic field of inorganic nano material.In particular, the size control that relates to a kind of hydro-thermal or solvent thermal carbon-coated nano molybdenum dioxide material is synthesized.
Background technology
Molybdenum dioxide material has the features such as low metallic resistance, high chemical stability and environmental friendliness.It has important application in a lot of research fields, comprises sensor, electrochromic device, lithium ion battery, ultracapacitor and solar cell etc., thereby is more and more subject to investigator's extensive concern.Nanometer titanium dioxide Mo is because it is more conducive to the conduction of electronics and the transmission of ion, thereby there is potential using value in electrochemical field, comprise that negative material as lithium ion battery is (as document 1:J.H.Ku, Y. S.Jung, K.T.Lee, C.H.Kim and S.M.Oh, Journal of the Electrochemical Society 2009,156, A688 and document 2:Q.S.Gao, L.C.Yang, X.C.Lu, J.J.Mao, Y.H.Zhang, Y. P.Wu and Y.Tang, Journal of Materials Chemistry 2010,20,2807).Synthesizing of carbon-coated nano molybdenum dioxide material is more conducive to improve electric conductivity and the chemical stability of material in electrochemical applications.
The main preparation methods of nanometer titanium dioxide Mo comprises that thermal evaporation under high-temperature gas reduction method, inert atmosphere, solution reduction are synthetic etc.Yet the size of nanometer titanium dioxide Mo prepared by most of method is all greater than 50nm, is unfavorable for the fast transport of current carrier in material application process, thereby limited its raising at electrochemical applications performance.The conductivity of nanometer titanium dioxide Mo own has much room for improvement in actual applications simultaneously.And the preparation of small size carbon-coated nano molybdenum dioxide material not only can utilize the electroconductibility of the coated effectively raising of carbon material but also can utilize little nano-scale to realize the reinforcement utilization of current carrier, thereby become the difficult point in field of nano material preparation.
Summary of the invention
The object of the invention is to overcome the deficiency in above-mentioned existing technology of preparing a kind of method that provides small size carbon-coated nano molybdenum dioxide material to prepare.
The invention provides a kind of small size carbon-coated nano molybdenum dioxide material and method prepared, the method adopt environmental protection and the reductibility carbohydrate that is easy to get as difunctional dose, as the gentle reductive agent of molybdenum precursor again as the precursor of carbon, thereby utilize hydro-thermal or solvent-thermal method one step to prepare the small size carbon-coated nano molybdenum dioxide material that size can modulation.
A method of preparing carbon-coated nano molybdenum dioxide material, step is as follows:
1) in solvent, add reductibility carbohydrate and molybdenum precursor, form mixture; The ratio of reductibility carbohydrate and molybdenum precursor is pressed mole number and the Mo of reducing sugar
6+the ratio of mole number be 1:1-10:1, the quality sum of carbohydrate and molybdenum precursor and the mass ratio of solvent are 1:2-1:50.
2) mixture being packed in reactor, is crystallization at 100 ℃-250 ℃ in Heating temperature; After crystallization time 2h – 48h, by aforesaid reaction vessel cool to room temperature, obtain the product after crystallization.
3) water or dimethyl formamide clean the product obtaining after crystallization, and then centrifugation makes carbon-coated nano molybdenum dioxide material.
Described solvent is one or more the mixture being selected from water, ethanol and acetone.
Described reductibility carbohydrate is one or more the mixture being selected from glucose, fructose, semi-lactosi, lactose, maltose.
Described molybdenum precursor is one of molybdic oxide, Sodium orthomolybdate, phospho-molybdic acid or ammonium molybdate.
The coated molybdenum dioxide material of prepared small size carbon is nano bar-shape structure, the wide 50nm that is all less than of rod.
Effect of the present invention is: can prepare the coated molybdenum dioxide nano bar-shape material of small size (the wide 50nm of being less than of rod) carbon, by changing the ratio of carbohydrate and molybdenum precursor, the change temperature of crystallization or the time of crystallization can be controlled the size of material.That the inventive method has is simple to operate, raw material is easy to get and eco-friendly feature.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope photo of the prepared carbon-coated nano molybdenum dioxide of embodiment 2 material;
Fig. 2 is embodiment 1,2,3 prepared carbon-coated nano molybdenum dioxide materials the diffraction contrast figure of XRD;
Fig. 3 is the transmission electron microscope photo of the prepared carbon-coated nano molybdenum dioxide of embodiment 4 material;
Fig. 4 is the transmission electron microscope photo of the prepared carbon-coated nano molybdenum dioxide of embodiment 5 material.
Embodiment
In 40ml water, add 1.0g fructose and 1.1g Sodium orthomolybdate (Na
2moO
4), form mixture (mole number of reducing sugar and Mo
6+the ratio of mole number be 1:1, the quality sum of carbohydrate and molybdenum precursor and the mass ratio of solvent are 1:19); Mixture is packed in reactor, is crystallization at 160 ℃ in Heating temperature; After crystallization time 4h, by aforesaid reaction vessel cool to room temperature, obtain the product after crystallization; Water cleans the product obtaining after crystallization, and then centrifugation makes carbon-coated nano molybdenum dioxide material.Its XRD diffractogram is shown in shown in 1 in Fig. 2, and the peak position of diffraction peak and peak intensity are consistent with the JCPDS card (32-0671) of XRD diffraction peak database, visible preparation-obtained is the MoO of monocline
2product.
In 20ml ethanol, add 0.5g glucose and 0.4g molybdic oxide (MoO
32H
2o), form mixture (mole number of reducing sugar and Mo
6+the ratio of mole number be 1.25:1, the quality sum of carbohydrate and molybdenum precursor and the mass ratio of solvent are 1:17.5); Mixture is packed in reactor, is crystallization at 160 ℃ in Heating temperature; After crystallization time 12h, by aforesaid reaction vessel cool to room temperature, obtain the product after crystallization; Water cleans the product obtaining after crystallization, and then centrifugation makes carbon-coated nano molybdenum dioxide material.Its XRD diffractogram is shown in shown in 3 in Fig. 2, and the peak position of diffraction peak and peak intensity are consistent with the JCPDS card (32-0671) of XRD diffraction peak database, visible preparation-obtained is the MoO of monocline
2product; Its transmission electron microscope photo as shown in Figure 1, is visible as wide about 5nm, the long rod-like nano molybdenum dioxide material that is less than 45nm.
In 60ml acetone, add 2.8g maltose and 1.2g ammonium molybdate ((NH
4)
6mo
7o
244H
2o), form mixture (mole number of reducing sugar and Mo
6+the ratio of mole number be 1.20:1, the quality sum of carbohydrate and molybdenum precursor and the mass ratio of solvent are 1:12); Mixture is packed in reactor, is crystallization at 160 ℃ in Heating temperature; After crystallization time 22h, by aforesaid reaction vessel cool to room temperature, obtain the product after crystallization; Water cleans the product obtaining after crystallization, and then centrifugation makes carbon-coated nano molybdenum dioxide material.Its XRD diffractogram is shown in shown in 3 in Fig. 2, and the peak position of diffraction peak and peak intensity are consistent with the JCPDS card (32-0671) of XRD diffraction peak database, visible preparation-obtained is the MoO of monocline
2product.
Embodiment 4
In 835ml water, add 16g lactose and 0.7g phospho-molybdic acid (H
3pO
412MoO
3), form mixture (mole number of reducing sugar and Mo
6+the ratio of mole number be 10:1, the quality sum of carbohydrate and molybdenum precursor and the mass ratio of solvent are 1:50); Mixture is packed in reactor, is crystallization at 250 ℃ in Heating temperature; After crystallization time 2h, by aforesaid reaction vessel cool to room temperature, obtain the product after crystallization; Water cleans the product obtaining after crystallization, and then centrifugation makes carbon-coated nano molybdenum dioxide material.Its transmission electron microscope picture as shown in Figure 3, is visible as wide about 3nm, the long rod-like nano molybdenum dioxide material that is less than 25nm.
Embodiment 5
In 16ml water, add 4g glucose and 4g molybdic oxide (MoO
32H
2o), form mixture (mole number of reducing sugar and Mo
6+the ratio of mole number be 1:1, the quality sum of carbohydrate and molybdenum precursor and the mass ratio of solvent are 1:2); Mixture is packed in reactor, is crystallization at 100 ℃ in Heating temperature; After crystallization time 48h, by aforesaid reaction vessel cool to room temperature, obtain the product after crystallization; Water cleans the product obtaining after crystallization, and then centrifugation makes carbon-coated nano molybdenum dioxide material.Its transmission electron microscope picture as shown in Figure 4, is visible as wide about 4nm, the long rod-like nano molybdenum dioxide material that is less than 15nm.
Although above-described embodiment is the embodiment of concrete point value, each example is applicable to following scope:
1) ratio of reductibility carbohydrate and molybdenum precursor is pressed mole number and the Mo of reducing sugar
6+the ratio of mole number be 1:1 – 10:1, the quality sum of carbohydrate and molybdenum precursor and the mass ratio of solvent are 1:2 – 1:50;
2) Heating temperature is crystallization at 250 ℃ of 100 ℃ –; After crystallization time 2h – 48h;
Solvent is one or more the mixture being selected from water, ethanol and acetone.
Reductibility carbohydrate is one or more the mixture being selected from glucose, fructose, semi-lactosi, lactose, maltose.
Molybdenum precursor is one of molybdic oxide, Sodium orthomolybdate, phospho-molybdic acid or ammonium molybdate.
Claims (3)
1. a method of preparing carbon-coated nano molybdenum dioxide material, is characterized in that step is as follows:
1) in solvent, add reductibility carbohydrate and molybdenum presoma, form mixture; The ratio of reductibility carbohydrate and molybdenum presoma is by mole number and the Mo of reductibility carbohydrate
6+the ratio of mole number be 1:1 – 10:1, the quality sum of reductibility carbohydrate and molybdenum presoma and the mass ratio of solvent are 1:2 – 1:50;
2) mixture being packed in reactor, is crystallization at 250 ℃ of 100 ℃ – in Heating temperature; After crystallization time 2h – 48h, by aforesaid reaction vessel cool to room temperature, obtain the product after crystallization;
3) water or dimethyl formamide clean the product obtaining after crystallization, and then centrifugation makes carbon-coated nano molybdenum dioxide material, and material is nano bar-shape structure, the wide 50nm that is less than of rod;
Reductibility carbohydrate is to be selected from a kind of in fructose, semi-lactosi, lactose, maltose.
2. the method for claim 1, is characterized in that described solvent is to be selected from a kind of in water, ethanol and acetone.
3. the method for claim 1, is characterized in that described molybdenum presoma is molybdic oxide, Sodium orthomolybdate, phospho-molybdic acid or ammonium molybdate.
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| CN106920957B (en) * | 2017-04-24 | 2019-10-25 | 陕西科技大学 | A kind of molybdenum dioxide nano particle and preparation method thereof for lithium ion battery negative material |
| CN113275002B (en) * | 2021-05-18 | 2022-07-29 | 杭州师范大学 | C/MoO 2 Porous photocatalyst and preparation method and application thereof |
| CN115367801B (en) * | 2022-07-07 | 2023-11-21 | 河南科技大学 | Near-spherical molybdenum disulfide-carbon composite material for lithium ion battery cathode and preparation method thereof |
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